Vinyl chloride resin composition

ABSTRACT

A vinyl chloride resin composition comprising a vinyl chloride polymer and glass fibers coated with a resin obtained by melting a component comprising the following (a) to (c): (a) a polymer miscible with the vinyl chloride polymer, (b) a crystalline polymer immiscible with the vinyl chloride polymer, and (c) a peroxide; a vinyl chloride resin composition comprising a vinyl chloride polymer and glass fibers coated with a copolymer (e) resin having a polymer chain immiscible with the vinyl chloride polymer and a polymer chain miscible with the vinyl chloride polymer; a vinyl chloride resin composition comprising a vinyl chloride polymer, the copolymer (e) and glass fibers coated with a resin miscible with the vinyl chloride polymer.

TECHNICAL FIELD

The present invention relates to a vinyl chloride resin compositionwhich is excellent in moldability and which provides a molded productexcellent in strength, impact strength, elastic modulus, moistureresistance and surface appearance.

BACKGROUND ART

A vinyl chloride resin and a vinyl chloride resin composition obtainedby blending a plasticizer to a vinyl chloride resin have such meritsthat they are relatively excellent in mechanical strength, and they canbe produced at a low cost. Accordingly, as resin materials for producinggeneral purpose molded products, they are used for various purposes suchas architectural parts, industrial parts and parts of electricalmachinery and apparatus. However, they have such demerits that for somepurposes, they are poor in heat resistance, mechanical strength,dimensional stability and thermal expansion.

To overcome these demerits, a study is being made to improve propertiesof a resin by alloying polymers having properties different from eachother. For example, there are various proposals for alloying a vinylchloride resin and an olefin resin (JP-B-60-36178, JP-A-63-604039,JP-A-1-165640, JP-A-2-199127, JP-A-2-199128, JP-A-2-199129 and thelike). However, the polymer alloy thus obtained is poor in elasticmodulus and heat resistance, since it contains an olefin resin.

On the other hand, it is known to incorporate glass fibers to a vinylchloride resin to strengthen and improve the properties of the vinylchloride resin. By this method, the rigidity and tensile strength can befairly improved, but the impact strength is often lowered.

Particularly, since a vinyl chloride resin is poorer in melt flowabilitythan other thermoplastic resins, the wettability with glass fibers isunsatisfactory, glass fibers are not dispersed evenly, and the meltflowability of the vinyl chloride resin wherein glass fibers are blendedis extremely low. As a result, there were such demerits as breaking downof glass fibers during kneading, heat deterioration of the resin, andparticularly a poor impact strength. Further, glass fibers come up tothe surface of a molded material, and the surface therefore becomescoarse. Accordingly, surface appearance becomes inferior. Thus,satisfactory properties could not be easily obtained.

To overcome the above demerits, there are, for example, such proposalsas (1) raising the molding temperature and (2) adding a lubricant, asurface modifying agent, or a resin miscible with a vinyl chloride resinhaving an excellent melt flowability, such as an ethylene-vinyl acetatecopolymer, an ethylene-vinylchloride copolymer or chlorinatedpolyethylene, to lower the viscosity of a vinyl chloride resin, as aresult, to improve the dispersibility and the wettability with glassfibers.

However, the above proposal (1) wherein the molding temperature israised, is not practical, because a vinyl chloride resin originally hasa molding temperature very close to the decomposition temperature, andit is therefore necessary to control the temperature strictly. Further,when adopting the above proposal (1), only a little rise of temperaturemakes the resin decomposed, and the mechanical strength of the moldedmaterial will be low.

The above proposal (2) wherein a resin is added so that the viscosity ofa vinyl chloride resin is lowered, needs an addition of a large amountof resin to get a satisfactory level of viscosity, and it substantiallychanges the original characteristic of a vinyl chloride resin.

Therefore, the above proposal (2) has such demerits as the loss of suchmerit that the mechanical strength of a resin is improved by addingglass fibers.

Further, it is known that glass fibers are added from a vent hole or adie of an extruder to prevent the glass fibers from being broken downduring molding and to improve the mechanical strength of a moldedproduct. In accordance with this method, the glass fibers are not brokendown, but the wetting between the resin and the glass fibers is notsufficient. Accordingly, this method has demerits such as the loss ofthe mechanical strength and particularly the remarkable loss of themoisture resistance.

To overcome these demerits, there are the following proposals (1) and(2). The proposal (1) disclosed in JP-B-49-6830, JP-B-49-13209 andJP-B-49-27663 is that such a vinyl monomer as vinyl chloride, vinylacetate or an aromatic vinyl is polymerized in the presence of glassfibers, glass fibers are coated with the polymer made of such a monomer,and the glass fibers coated with the polymer are kneaded and mixed witha vinyl chloride resin to obtain a molded product. The proposal (2)disclosed in JP-A-6-65427 is that a compatibilizing agent is added toimprove the properties of a polymer alloy.

In accordance with these methods, the adhesion property between a resinand glass fibers is improved, and the surface appearance and severalkinds of mechanical strength of the molded product are improved alittle, but these methods are not always satisfactory because the impactstrength, the elastic modulus, the moisture resistance and themoldability are not balanced well. Since these methods include a batchpolymerization reaction using a monomer, it takes much time for theproduction, a continuous production is impossible, and there istherefore an economical problem. Further, the length of the glass fibersto be used is restricted in practical production, and these methods aretherefore disadvantageous.

The present invention overcomes the above-mentioned demerits of priorart, and it provides a polyvinyl chloride resin composition which isexcellent in moldability, mechanical strength such as impact strength,and surface appearance.

DISCLOSURE OF THE INVENTION

The present inventors have studied and discovered that a vinyl chlorideresin comprising glass fibers coated with a resin obtained by melting acomponent comprising a polymer miscible with a polyvinyl chloride, acrystalline polymer immiscible with a polyvinyl chloride, and aperoxide, is improved in such mechanical strength as impact strength,strength, elastic modulus and moisture resistance. Further, the presentinventors surprisingly discovered that the moldability and the surfaceappearance are remarkably improved. This is the gist of the presentinvention, as described below.

A composition comprising 100 parts by weight of a vinyl chloride polymer(A) and 10 to 200 parts by weight of coated glass fibers (1) coated witha coating resin obtained by melting a component comprising a polymer (a)miscible with the vinyl chloride polymer, a crystalline polymer (b)immiscible with the vinyl chloride polymer, and a peroxide (c).

A composition comprising 100 parts by weight of a vinyl chloride polymer(A) and 10 to 200 parts by weight of coated glass fibers (2) coated witha coating resin of a copolymer (e) having a polymer chain (X) immisciblewith the vinyl chloride polymer (A) and a polymer chain (Y) misciblewith the vinyl chloride polymer in the same molecule.

A composition comprising 100 parts by weight of a vinyl chloride polymer(A), 1 to 15 parts by weight of the copolymer (e) having a polymer chain(X) immiscible with the vinyl chloride polymer and a polymer chain (Y)miscible with the vinyl chloride polymer in the same molecule, and 10 to150 parts by weight of coated glass fibers (3) coated with a coatingresin of a thermoplastic resin miscible with the vinyl chloride polymer.

The basic technical concept of the present invention resides in acomposition comprising a vinyl chloride polymer, a polymer immisciblewith the vinyl chloride polymer, a polymer miscible with the vinylchloride polymer, and glass fibers.

The polymer immiscible with the vinyl chloride polymer and the polymermiscible with the vinyl chloride polymer are characterized in that theyare used as a copolymer (1) obtained by melting and graft-polymerizing acomponent comprising the immiscible polymer and the miscible polymer, oras a copolymer (2) having a polymer chain of a monomer to form animmiscible homopolymer and a polymer chain of a monomer to form amiscible homopolymer in the same molecule.

That is, in order to make the polymers immiscible and miscible with thevinyl chloride polymer fulfill their functions effectively, a polymerhaving both of these characters in the same molecule is used.

Further, it is important that the glass fibers are basically coated witha thermoplastic resin miscible with the vinyl chloride polymer or with aresin having a polymer chain of a monomer to form a misciblehomopolymer.

It is a feature that as the resin miscible with the vinyl chloridepolymer, a thermoplastic resin miscible with the vinyl chloride polymer,the above copolymer (1), or the above copolymer (2) is used as thecoating resin for glass fibers.

With regard to the vinyl chloride polymer (A)!

The vinyl chloride polymer (A) used in the present invention is obtainedby a well known method, i.e. a suspension polymerization method, anemulsion polymerization method, or a bulk polymerization method. Theaverage degree of polymerization of the vinyl chloride polymer (A) ispreferably 400 to 1,500, and is more preferably 450 to 1,000. If theaverage degree of polymerization is too small, it is observed thatmechanical properties such as impact strength and elastic modulus andheat stability deteriorate, such being undesirable. If the averagedegree of polymerization is too large, the melt flowability deterioratesremarkably and molding will be too difficult.

Here, the vinyl chloride polymer polymer (A) is substantially a vinylchloride polymer wherein at least 60% by weight of the constitutivecomponents are polymer units based on vinyl chloride. Specifically, avinyl chloride homopolymer, an ethylene-vinyl chloride copolymer, avinyl acetate-vinyl chloride copolymer, a graft copolymer of anethylene-vinyl acetate copolymer and a vinyl chloride polymer, and achlorinated polyvinyl chloride may be mentioned. One or a combination oftwo or more selected from these polymers is used.

With regard to the polymer (a) miscible with the vinyl chloride polymer(A)!

The term "miscible" is a state wherein the vinyl chloride polymer (A)and the miscible polymer are mixed with each other in molecular ordersin a thermodynamically stable state, or is a character wherein a certainaffinity acts to the interface and a stable micro phase separation stateis obtained. Accordingly, when the polymer (a) is the vinyl chloridepolymer (A), it is mixed substantially homogeneously. When the polymer(a) is miscible with the vinyl chloride polymer (A) to some extent, itcan be dispersed stably in the continuous phase of the vinyl chloridepolymer (A) in a particle state wherein the particle size is, forexample, 0.01 to 10 μm.

That is, when the coated glass fibers containing the polymer (a) areblended and melt-kneaded with the vinyl chloride polymer (A), it can berapidly dispersed homogeneously in the vinyl chloride polymer (A)together with the glass fibers, and it can improve the mechanicalstrength such as impact strength, strength, elastic modulus and moistureresistance remarkably due to the affinity of the interface with thematrix vinyl chloride polymer (A).

There is no particular restriction with regard to the molecular weightof the polymer (a). However, if the molecular weight is too large, it isnot completely miscible with other components, such being undesirable.The average molecular weight is therefore preferably 1,000 to 400,000.

Hereinafter, the monomer to form a homopolymer immiscible with the vinylchloride polymer (A) will be referred to as the monomer (m), and themonomer to form a homopolymer miscible with the vinyl chloride polymer(A) will be referred to as the monomer (n). The units derived from sucha monomer and constituting a polymer will be referred to as polymerunits. The polymer units derived from the monomer (m) will be referredto as the polymer units (m), and the polymer units derived from themonomer (n) will be referred to as the polymer units (n). Further,specific polymer units will be named by adding the term "polymer units"to the name of the monomer (for example, "propylene polymer units" orthe like).

The polymer (a) contains the polymer units (n) miscible with the vinylchloride polymer (A). However, as far as the polymer (a) is as a wholemiscible with the vinyl chloride polymer (A), it may contain otherpolymer units. Such other polymer units may, for example, be polymerunits other than the polymer units (n) and the polymer units (m), orpolymer units which can be hardly identified with either one of these.The polymer (a) may contain two or more different kinds of the polymerunits (n). The same applies when the polymer (a) contains the polymerunits (m) or other polymer units.

The monomer (n) may, for example, be a vinyl chloride monomer, anacrylic acid type monomer such as an acrylic acid alkyl ester typemonomer, a methacrylic acid type monomer such as a methacrylic acidalkyl ester type monomer or a vinyl cyanide type monomer.

The vinyl cyanide type monomer forms a polymer highly miscibleparticularly with the vinyl chloride polymer (A). However, since thehomopolymer of the same is insufficient in the physical properties, itis preferably copolymerized with other monomers to form the polymer (a).

The polymer (a) may, for example, be the above-mentioned vinyl chloridepolymer (A), a copolymer of a vinyl cyanide type monomer and an aromaticvinyl type monomer, an acrylic acid alkyl ester polymer, a methacrylicacid alkyl ester polymer, or a vinyl acetate polymer.

More specifically, the copolymer of a vinyl cyanide type monomer and anaromatic vinyl type monomer is a copolymer obtained by copolymerizing avinyl cyanide type monomer such as acrylonitrile or methacrylonitrile,and an aromatic type vinyl monomer such as styrene, α-methyl styrene,vinyl toluene or chlorostyrene. The ratio of the polymer units based onthe vinyl cyanide type monomer in the copolymer is preferably 5 to 80%by weight and is more preferably 10 to 50% by weight.

If the ratio of the vinyl cyanide polymer units is small, themiscibility with the vinyl chloride polymer (A) tends to be low, wherebyit can not sufficiently be dispersed in the matrix vinyl chloridepolymer (A), and the mechanical strength of the resulting molded productwill be low, and the affinity with the glass fibers will beinsufficient, whereby the moisture resistance of the resulting moldedproduct will be poor, such being undesirable. As this copolymer, anacrylonitrile-styrene copolymer is particularly preferred.

The acrylic acid alkyl ester polymer or the methacrylic acid alkyl esterpolymer is preferably a polymer of a monomer wherein the carbon numberof the alkyl moiety is at most 4. If the carbon number of the alkylmoiety is 5 or larger, the miscibility of the polymer with the vinylchloride polymer (A) tends to be low, such being undesirable for thesame reasons as mentioned above. Particularly preferred is themethacrylic acid alkyl ester type monomer.

Preferred is one or more kinds of such methacrylic acid alkyl ester typemonomer, a combination of this methacrylic acid alkyl ester type monomerand another methacrylic acid alkyl ester type monomer, or a combinationof this methacrylic acid alkyl ester type monomer and a monomer otherthan the methacrylic acid alkyl ester type monomer.

Specifically, polymethyl acrylate, polymethyl methacrylate, polyethylacrylate and polyethyl methacrylate may be mentioned. A particularlypreferred polymer is polymethyl methacrylate.

The vinyl acetate polymer includes a vinyl acetate homopolymer and anethylene-vinyl acetate copolymer. With regard to the ethylene-vinylacetate copolymer, the ratio of the polymer units based on vinyl acetatemonomer is preferably at least 10% by weight. If it is less than 10% byweight, the miscibility with the vinyl chloride polymer (A) tends to below, such being undesirable for the same reasons as mentioned above.

As the polymer (a), it is more preferred to employ a polymer having aglass transition temperature higher than that of the vinyl chloridepolymer (A) from the viewpoint of the heat resistance represented by theheat distortion temperature when it is blended with a vinyl chlorideresin. An acrylonitrile-styrene copolymer or polymethyl methacrylate isparticularly preferred.

With regard to the crystalline polymer (b) immiscible with the vinylchloride polymer (A)!

The polymer (b) does not have an affinity to the interface with thevinyl chloride (A), can not form a stable micro phase separation state,and has crystallinity. The crystallinity used here is a character toshow a clear crystal melting point, for example, an endothermic peak ina thermal analysis such as DSC. That is, the crystallinity here is acharacter wherein the melt viscosity sharply decreases at saidtemperature, and does not necessarily mean a crystallinity of 100%.

The crystal melting point is preferably at most 250° C. which is closeto the processing temperature of the vinyl chloride polymer (A), and isparticularly preferably at most 200° C. Further, the lower limit ispreferably at least 80° C., and is particularly preferably at least 100°C. because the glass transition temperature is preferably higher thanthat of the vinyl chloride polymer (A) in view of mechanical strengthand heat resistance.

When the coated glass fibers are blended and melt-kneaded with the vinylchloride polymer (A), the polymer (b) moiety in the coating resin isessentially immiscible with the vinyl chloride polymer (A), and ittherefore slips on the molecular chain without being entangled with themolecular chain of the vinyl chloride polymer (A), that is, it exhibitsthe so-called slipping property. This is particularly remarkable whenthe crystal melting point does not exceed the processing temperature.Accordingly, the melt viscosity of the system can be lowered, themoldability and the surface appearance will be remarkably improved, andthe shear stress resulting from kneading will be lowered. As a result,breakage of the glass will be less and particularly the impact strengthcan be improved.

There is no particular restriction with regard to the molecular weightof the polymer (b). However, if the molecular weight is too large, itcan not sufficiently be kneaded with other components, such beingundesirable. The average molecular weight is therefore preferably 1,000to 400,000.

The polymer (b) contains the polymer units (m). However, as far as thepolymer (b) is as a whole immiscible with the vinyl chloride polymer(A), it may contain the polymer units (n) or other polymer units. As faras the polymer units (m) are polymer units substantially immiscible withthe vinyl chloride polymer (A), they are not restricted. For example, itis a homopolymer of ethylene, propylene or other α-olefin, or acombination of these monomers. Specifically, it is preferablypolyethylene or polypropylene, and is particularly preferablypolypropylene.

With regard to the blending ratio of the polymer (a) and the polymer(b)!

With regard to the blending ratio of the polymer (a) and the polymer(b), to the total of both, the former is in the range of 95 to 5% byweight and the latter is in the range of 5 to 95% by weight.Particularly preferably, the former is in the range of 80 to 20% byweight and the latter is in the range of 20 to 80% by weight. If eitherone of these is less than 5% by weight, the above-mentioned effects ofeither the polymer (a) or the polymer (b) can not be achieved.

With regard to the peroxide (c)!

The peroxide (c) can be decomposed by heat to produce free radicals, andknown organic peroxides can be used. Specifically, the followingexamples may be given.

Ketone peroxides such as cyclohexanone peroxide and methylethylketoneperoxide, hydroperoxides such as 1,1,3,3-tetramethylbutylhydroperoxideand t-hexylhydroperoxide, dialkylperoxides such as dicumylperoxide and1,3-bis(t-butylperoxyisopropyl)benzene, diacylperoxides such asbenzoylperoxide and lauroylperoxide, peroxydicarbonates such asdiisopropylperoxydicarbonate and di-n-propylperoxydicarbonate,peroxyesters, peroxyketals, and the like.

With regard to the decomposition temperature, it is necessary that freeradicals can be formed at a temperature under which a coating resin isobtained. The temperature of 10 hour-half period is preferably 70° to150° C. in view of handling, although it depends on conditions.

The free radicals generated from peroxides during melting can beexpected to provide the following functions:

(1) A molecular chain of the polymer (a) and/or the polymer (b) is cut,the melt viscosity of the system is lowered, and the impregnationproperty to the glass fibers is improved.

(2) At the same time, by a reaction for withdrawing hydrogen or the likefrom the polymer (a) and the polymer (b), new radicals will be formed atthe molecular chain. Starting from the new radicals, a copolymer isconsidered to be produced by a reaction between the polymer (a) and thepolymer (b). Said copolymer acts as a compatibilizing agent for theremaining polymer (a) and the polymer (b), and it makes mixing easy.

(3) When the below-mentioned monomer (d) coexists, a reaction startsfrom the new radicals formed at the monomer (d), the polymer (a) and/orthe polymer (b), to form a copolymer which is able to firmly bond to theglass fibers.

These functions are particularly remarkable when the polymer (b) ispolypropylene. When the coating resin obtained by melting the componentcomprising the polymer (a), the polymer (b) and the peroxide (c) iscoated on the glass fibers, the melt viscosity of the coating resin in amelt state is preferably at most 1,000 poise to facilitate impregnationto the glass fibers. To the component comprising the polymer (a), thepolymer (b) and the peroxide (c), various ingredients may be blended.For example, a surface treatment agent for glass fibers such as thebelow-mentioned silane coupling agent or a lubricant can be blended.

The amount of the peroxide to be added is determined depending on themelt viscosity of the coating resin in a melt state. If the amount to beadded is too large, the reaction becomes complicated, and such isundesirable also from the viewpoint of operation, safety and economy. Itis preferably within a range of 0.1 to 10 parts by weight, per 100 partsby weight of the total of the polymer (a) and the polymer (b).

With regard to the monomer (d) to improve the adhesion to the glassfibers!

The monomer (d) can be used together with the polymer (a), the polymer(b) and the peroxide (c) to improve the adhesion between the glassfibers and the vinyl chloride polymer (A) and to improve the physicalproperties of the composition of the present invention. That is, by theaction of the free radicals formed by the peroxide (c), the monomer (d)reacts with the polymer (a) and/or the polymer (b), to form a copolymerwhich is able to firmly bond to the glass fibers. The monomer (d) ispreferably a vinyl monomer having a functional group. The functionalgroup may, for example, be an epoxy group, a carboxyl group, acarboxylic anhydride group, an amino group, a silyl group having ahydrolyzable group, and an amide group or a hydroxyl group. Particularlypreferred is an epoxy group, a carboxyl group or a carboxylic anhydridegroup.

The vinyl monomer having an epoxy group may, for example, be a glycidylester such as glycidyl acrylate, glycidyl methacrylate or glycidylitaconate, or a glycidyl ether such as vinyl glycidyl ether or allylglycidyl ether. Particularly preferred is glycidyl methacrylate or vinylglycidyl ether. The vinyl monomer having a carboxyl group may, forexample, be acrylic acid, methacrylic acid, itaconic acid or maleicacid. Particularly preferred is methacrylic acid or maleic acid. Thevinyl monomer having a carboxylic anhydride group may be an unsaturatedpolybasic carboxylic anhydride which is an anhydride of a polybasiccarboxylic acid having a polymerizable unsaturated group, such as maleicanhydride, itaconic anhydride or endic anhydride. Particularly, maleicacid anhydride is preferable.

If the amount of the monomer (d) is too large, the monomer (d) tends toinitiate a secondary reaction against the polymer (a) and the polymer(b), such being undesirable, and a network structure is formed by acrosslinking reaction, whereby the resin becomes hardly meltable, andthe dispersibility of the glass fibers will deteriorate remarkably.Accordingly, the suitable amount to be used is 0.1 to 20 parts by weightto 100 parts by weight of the total of the component comprising thepolymer (a), the polymer (b) and the peroxide (c).

With regard to the copolymer (e)!

The copolymer (e) can be used alone to coat the glass fibers. It canalso be used together with the polymer (a), the polymer (b) and theperoxide (c). In this case, the above-mentioned monomer (d) can be alsoused together. Since the polymer chain (X) which is a constitutivecomponent of the copolymer (e), is immiscible with the vinyl chloridepolymer (A) like the polymer (b), and the polymer chain (Y) is misciblewith the vinyl chloride polymer (A) like the polymer (a), it issubstantially a structure having the above-mentioned polymer (a) andpolymer (b) in one same molecular. Accordingly, the copolymer which isconsidered to be formed by the partial reaction between the polymer (a)and the polymer (b), is considered to be essentially the same structureas the copolymer (e).

However, the characters of the polymer (a) and the polymer (b) arecompletely opposite to each other against the vinyl chloride polymer(A), and these two polymers are essentially poor in miscibility to eachother. If the difference in the melt viscosity between these twopolymers is remarkably large when coating the glass fibers, it becomesmore difficult to mix them homogeneously, the coated state of glassfibers will be non-uniform, and the reproducibility of the propertiessometimes tends to be poor.

Accordingly, when such a phenomenon is evident from the combination ofthe selected polymers (a) and (b), the copolymer (e) may be used toobtain a coating resin, so that it serves as a compatibilizing agent forthe polymer (a) and the polymer (b), and they can be homogeneously mixedvery easily during the early period of melt-kneading.

In this case, it is more preferable that the polymer chain (X) has thesame structure as the polymer (b), and the polymer chain (Y) has thesame structure as the polymer (a), because such an action can beremarkably demonstrated. It is, therefore, not necessary to use it in alarge amount, and 0.1 to 20 parts by weight to 100 parts by weight ofthe component comprising the polymer (a), the polymer (b) and theperoxide (c) is a suitable amount. When it is used alone to coat theglass fibers, 5 to 60 parts by weight to the coated glass fibers is asuitable amount.

The length of the polymer chain (X) in the copolymer (e) is notparticularly restricted, so long as it is immiscible with the vinylchloride polymer (A). Similarly, the length of the polymer chain (Y) isnot particularly restricted, so long as it is miscible with the vinylchloride polymer (A). However, a polymer wherein the polymer units toconstitute an immiscible polymer and the polymer units to constitute amiscible polymer are polymerized alternately is not preferable for thecopolymer (e), and a polymer wherein these polymer units are polymerizedat random is not preferable for the copolymer (e), either.

Therefore, the copolymer (e) is preferably a block copolymer or a graftcopolymer having one or more of the polymer chain (X) and the polymerchain (Y) respectively, and is more preferably a combination wherein thepolymer chain (X) is structurally the same as the polymer (b) and thepolymer chain (Y) is structurally the same as the polymer (a). In caseof the graft copolymer, the polymer chain (X) may be either a straightchain or a branched chain. However, the graft copolymer wherein thepolymer chain (X) is a straight chain and the polymer chain (Y) is abranched chain is preferred in view of the effect of the invention andthe easiness of production.

With regard to the ratio of the polymer chain (X) and the polymer chain(Y) to constitute the copolymer (e), the former is in the range of 95 to5% by weight and the latter is in the range of 5 to 95% by weight. It isparticularly preferred that the former is in the range of 80 to 20% byweight, and the latter is in the range of 20 to 80% by weight.

The above range is preferred because it is effective as acompatibilizing agent for the polymer (a) and the polymer (b). There isno particular restriction with regard to the molecular weight of thecopolymer (e). The average molecular weight is preferably 1,000 to400,000, and is particularly preferably 2,000 to 200,000.

With regard to specific examples of the polymer chain (X)!

The polymer chain (X) consists of a chain containing the polymer units(m). A relatively small amount of the monomer (n) or other monomers maybe copolymerized with the monomer (m). However, the polymer chain (X) ispreferably a polymer chain consisting essentially of one or more kindsof the monomer (m) only, and is more preferably a polymer chain havingthe same structure as the polymer (b).

Accordingly, the monomer (m) is preferably ethylene or propylene asdescribed with regard to the polymer (b), and is particularly preferablypropylene.

With regard to specific examples of the polymer chain (Y)!

The polymer chain (Y) consists of a chain containing the polymer units(n), and the monomer (m) and other monomers may be copolymerized withthe monomer (n). The polymer chain (Y) to be formed is more preferablyselected from the monomer (n) and a combination of the monomer (n) andthe monomer (m), to have substantially the same structure as the polymer(a). As described with regard to the polymer (b), the monomer (n) istherefore a vinyl chloride monomer, an acrylic acid type monomer such asan acrylic acid alkyl ester type monomer, a methacrylic acid typemonomer such as a methacrylic acid alkyl ester type monomer, or a vinylcyanide type monomer.

The monomer to form the polymer chain (Y) is particularly preferably acombination of acrylonitrile-styrene, or methyl methacrylate.

In the polymer chain (Y) comprising vinyl cyanide polymer units andaromatic vinyl polymer units, the ratio of the vinyl cyanide polymerunits is, like in the polymer (a), preferably 5 to 80% by weight, and isparticularly preferably 10 to 50% by weight, in the polymer chain (Y).

The method for producing the copolymer (e) is not particularlyrestricted, and a known method can be used. For example, a method may bementioned wherein one or more kinds of the monomer (n) are reacted to apolymer obtained by polymerizing one or more kinds of the monomer (m),at a predetermined temperature, for example, 150° to 250° C. using aradical initiator such as benzoyl peroxide or dicumyl peroxide, toobtain a graft copolymer. In the polymerization reaction, a solvent suchas toluene or xylene can be used if necessary.

Further, there is a method wherein after living-polymerizing one or morekinds of the monomer (m), one or more kinds of the monomer (n) arereacted thereto to obtain a block copolymer directly, or a methodwherein a polymer obtained by polymerizing one or more kinds of themonomer (m) and a polymer obtained by polymerizing one or more kinds ofthe monomer (n), are polymerized separately, to introduce at one end ofeach polymer, a carboxyl group or an isocyanate group, and at the otherend, a hydroxyl group or an amino group, and then, these modifiedpolymers are reacted with each other to obtain the copolymer (e).

With regard to the thermoplastic resin!

The thermoplastic resin to coat the glass fibers preferably consists ofa polymer of a functional group-containing vinyl monomer with a monomerto form a polymer miscible with a vinyl chloride polymer. The functionalgroup enhances the bonding between the glass fibers and a polymer suchas the vinyl chloride polymer or the copolymer (e), and improves thephysical properties of the composition of the present invention. Thefunctional group may, for example, be an epoxy group, a carboxyl group,a carboxylic anhydride group, an amino group, a silyl group having ahydrolyzable group, an amide group or a hydroxyl group. Particularlypreferred is an epoxy group, a carboxyl group, or a carboxylic anhydridegroup.

The thermoplastic resin is preferably a copolymer of a monomer having nofunctional group and a vinyl monomer having a functional group. However,it is not restricted to this, and it may be a thermoplastic resinobtained by introducing a functional group into a polymer having nofunctional group by a post-treatment. It is preferably the copolymercomprising 99.5 to 50% by weight of the monomer to form a polymermiscible with the vinyl chloride polymer and 0.5 to 50% by weight of thevinyl monomer having a functional group. If the latter ratio is lessthan 0.5% by weight, the impact strength will not be improved. If itexceeds 50% by weight, the miscibility with the vinyl chloride polymertends to deteriorate, whereby the flowability or the dispersibility ofglass fibers will be low, such being undesirable.

The monomer to form a polymer miscible with the vinyl chloride polymerto form the thermoplastic resin may be the above-mentioned monomer (n)or a combination of the monomer (n) and the monomer (m). However, it isnot necessarily the same as the monomer (n) selected for the copolymer(e). In addition to the above illustrated monomers for the monomer (n),vinyl acetate, a combination of vinyl acetate-ethylene, and acombination of vinyl acetate-vinyl chloride are preferred.

The vinyl monomer having a functional group is generally a monomer toform a homopolymer miscible with a vinyl chloride polymer, but it is notrestricted to this. The vinyl monomer having a functional group ispreferably the above-mentioned monomer (d), and it is particularlypreferably a vinyl monomer having a functional group selected from anepoxy group, a carboxyl group or carboxylic anhydride groups.Specifically, the above-mentioned monomers illustrated for the monomer(d) are preferred.

There is no particular restriction with regard to the molecular weightof the thermoplastic resin. However, if it is too large, thedispersibility of the glass fibers is poor when kneaded with the vinylchloride polymer, such being undesirable. The average molecular weightis preferably 1,000 to 400,000.

With regard to the coated glass fibers!

As the glass fibers, it is preferred to use relatively long glass fiberssuch as roving fibers or chopped strand fibers. Particularly preferredare commercially available roving glass fibers. The diameter of theglass fibers is preferably 1 to 20 μm.

Further, the glass fibers may be surface-treated as usual by a surfacetreating agent such as a coupling agent, a film former or a lubricant.The coupling agent is, for example, a silane coupling agent which is asilane compound wherein a hydrolyzable group is bonded to a siliconatom. Specific silane coupling agents are as follows

A methacryl silane compound such as γ-methacryloxypropyltriethoxysilaneor γ-methacryloxypropylmethyldiethoxysilane, an epoxy silane compoundsuch as γ-glycidoxypropyltrimethoxysilane, an amino silane compound suchas γ-aminopropyltriethoxysilane orN-β-aminoethyl-γ-aminpropyltriethoxysilane, a vinyl silane compound suchas vinyltrimethoxysilane and a chlorosilane compound such asγ-chloropropyltrimethoxysilane.

The method for coating the coating resin to the glass fibers is notparticularly restricted. A method may be used wherein the componentcomprising the polymer (a), the polymer (b) and the peroxide (c) ismelt-mixed to form a coating resin in a melt state, and the coatingresin in a melt state is coated on the glass fibers. The coating resincan be cooled once and be melted again to be used for coating.

It is preferred to employ a method wherein roving glass fibers arecontinuously passed through the resin vessel packed with the coatingresin in a melt state, so that the coating resin is impregnated into andcoated on the glass fibers, followed by cutting. In this case, it ispreferred for continuous production to premix the component comprisingthe polymer (a), the polymer (b) and the peroxide (c) before heating, tomelt-knead it at an adequate temperature using an extruder, and tointroduce it into the coating resin vessel.

In this case, the amount to be extruded by the extruder depends on theamount of the glass fibers to be supplied in the coating resin vessel.The temperature of the coating resin vessel is preferably adjusted sothat the melt viscosity of the coating resin in a melt state is at most1,000 poise, particularly at most 500 poise. If the melt viscosity ofthe coating resin exceeds 1,000 poise, it becomes difficult for thecoating resin to impregnate into the roving glass fibers, and when thecoated glass fibers (1) or (2) are blended with the vinyl chloridepolymer (A), dispersion of the glass fibers tends to be insufficient,whereby the mechanical strength will not be improved, and the surfaceappearance of the molded product will be substantially impaired, suchbeing undesirable.

As the method for coating glass fibers with the thermoplastic resin,there is a method wherein the monomer of the resin is polymerized in thepresence of the glass fibers, a method wherein the resin in a melt stateis impregnated into the glass fibers, or a method wherein the solutionor the emulsion of the resin is impregnated and then the solvent isremoved therefrom. The method wherein the monomer is polymerized in thepresence of the glass fibers is particularly preferred.

Specifically, when the chopped strand glass fibers are used, suspensionpolymerization is conducted in the presence of both the glass fibers andthe monomer. On the other hand, when the roving glass fibers are used,it is preferred to employ a method wherein the glass fibers arecontinuously passed through the resin vessel in a melt state so that theresin is thereby impregnated into the glass fibers, and then cut.

The coated glass fibers obtained by the above-mentioned method have alength of preferably 1 to 50 mm in view of handling, more preferably 1to 20 mm.

The blending amount of the coated glass fibers (1) or (2) in thecomposition is 10 to 200 parts by weight to 100 parts by weight of thevinyl chloride polymer (A). If it is less than 10 parts by weight,various properties of the vinyl chloride resin will not sufficiently bestrengthened or improved. If it exceeds 200 parts by weight, theefficiency of adding the glass fibers will not be improved so much andinversely the moldability will extremely deteriorate.

The blending amount of the coated glass fibers (3) in the composition is10 to 150 parts by weight to 100 parts by weight of the vinyl chloridepolymer (A). If it is less than 10 parts by weight, various propertiesof the vinyl chloride resin will not sufficiently be strengthened orimproved. If it exceeds 150 parts by weight, the efficiency of addingthe glass fibers will not be improved so much.

The amount of the coating resin in the coated glass fibers is preferablyat least 5% by weight in the coated glass fibers. If the amount of thecoating resin is less than 5% by weight, the glass fibers will not becompletely coated, and when it is kneaded with the vinyl chloridepolymer, the dispersibility of the glass fibers or the adhesion propertyto the vinyl chloride polymer tends to be insufficient. If the amount ofthe coating resin is too large, the ratio of the coating resin to allthe polymer components becomes high, and such is not advantageouseconomically and in view of deterioration of the physical properties.The amount of the coating resin is preferably at most 60% by weight,particularly preferably at most 40% by weight.

The amount of the glass fibers in the composition of the presentinvention is preferably 5 to 100 parts by weight to 100 parts by weightof the vinyl chloride polymer (A). If it is less than 5 parts by weight,various properties of the vinyl chloride resin will not sufficiently bestrengthened or improved. If it exceeds 100 parts by weight, theefficiency of adding the glass fibers will not be improved so much, andinversely the moldability will extremely deteriorate. The amount of thecoating resin coated with the glass fibers in the composition ispreferably at most 100 parts by weight, particularly preferably at most60 parts by weight, to 100 parts by weight of the vinyl chloridepolymer.

The composition of the present invention is preferably used as a moldingcomposition which will be subjected to molding. That is, the compositionwill be subjected to molding by itself or by further adding variousadditives. The molding method of the vinyl chloride resin compositionmay, for example, be injection molding, extrusion molding, pressmolding, or calender molding, which is applicable generally to athermoplastic resin and the like.

Specifically, powder or pellets of the composition is blended using aHenshel mixer or the like, and it is melt-kneaded at 150° to 180° C. bya single screw extruder or a twin screw extruder to obtain a moldedproduct. Particularly, it is preferably used for producing a moldedproduct by extrusion molding.

Together with the composition of the present invention, known additivessuch as a stabilizer for a vinyl chloride resin, an agent for improvingimpact strength, a lubricant, a pigment, an antistatic agent, an ageresistor, a filler, a blowing agent, and a fire retardant can be used,if necessary. The typical examples of these additives are as follows.

The stabilizer including such an organic tin heat stabilizer such asdibutyl tin mercaptide, dibutyl tin dilaurate or dibutyl tin distearate,a stabilizer of a fatty carboxylate such as barium stearate, calciumstearate or zinc stearate, an inorganic stabilizer, an epoxy compoundsuch as epoxidized soybean oil, an organic phosphate and an organicphosphite, the agent for improving impact strength including MBS resinand acrylic rubber, the lubricant including wax, a metallic soap and ahigher fatty acid such as stearic acid, the age resistor including aphenol antioxidant, a phosphite stabilizer and a ultraviolet rayabsorbent, and the filler including carbon black, hydrated calciumsilicate, silica, calcium carbonate and talc.

The total amount of these additives is, except for the filler,preferably at most 50 parts by weight to 100 parts by weight of thevinyl chloride polymer (A). Even if including the filler, the totalamount of these additives is preferably at most 100 parts by weight to100 parts by weight of the vinyl chloride polymer.

The shape of the molded product of the composition of the presentinvention is not particularly restricted. However, it is preferably anextruded molded product such as a plate-like, bar-like or tube-likeproduct having various shapes of cross sections. Typically, these areused as such architectural materials as a gutter, eaves, an externalwall siding material and a window frame, because these have suchproperties as strength, impact strength and elastic modulus, and theexpansion and contraction are extremely small due to the low coefficientof linear expansion.

In the present invention, the vinyl chloride polymer is blended with thecoated glass fibers coated with the coating resin obtained by meltingthe component comprising the polymer (a) miscible with the vinylchloride polymer, the crystalline polymer (b) immiscible with the vinylchloride polymer and the peroxide (c). Thereby, the melt property of thevinyl chloride resin is remarkably improved due to the slipping actionby the polymer (b), and the synergistic effect of the dispersibilityimproved by the polymer (a) in the matrix resin vinyl chloride polymerand the strengthened interface adhesion to the glass fibers is obtained.Accordingly, the present invention provides the vinyl chloride resincomposition wherein the strength, the impact strength, the elasticmodulus, the moisture resistance, the surface appearance and themoldability are remarkably improved, which could not be achieved by theprior art.

If coating is conducted with the coating resin of the copolymer (e)having the polymer chain (X) immiscible with the vinyl chloride polymerand the polymer chain (Y) miscible with the vinyl chloride polymer inthe same molecule, the glass fibers can be coated effectively anduniformly.

Further, by using the vinyl chloride polymer, the copolymer (e) and theglass fibers coated with the thermoplastic resin having a functionalgroup essentially miscible, the composition having the above-mentionedexcellent property can be obtained. The composition of the presentinvention is extremely useful for e.g. an extrusion molding composition.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be described in further detail with referenceto the Examples 1 to 10 and Comparative Examples 11 to 17, but it shouldbe understood that the present invention is by no means restricted tothese.

Preparation of the vinyl chloride polymer (A)!

3 parts by weight (hereinafter referred to simply as parts) of partiallysaponificated polyvinyl alcohol (Gosenol KH-20 made by Nihon GoseiKagaku), 0.5 part of azobisisobutylonitrile and 3,000 parts of purewater were added to a pressure reaction type reactor, anitrogen-replacement was conducted, and then 1,000 parts of vinylchloride monomer were added thereto. After conducting a reaction at 65°C. for 6 hours, the remaining monomer is removed, followed bydehydration-drying to obtain 950 parts of a polymer in a powder form.The degree of polymerization of the polymer thus obtained was 800.Hereinafter, this will be referred to as the polymer A.

Preparation of the coated glass fibers!

The components to be used for the coated glass fibers are as follows.

(a1) Acrylonitrile-styrene copolymer (containing 28% by weight ofacrylonitrile, melt index (hereinafter referred to as MI): 25 g/10min.),

(b1) polypropylene (crystal melting point: 165° C., MI: 13 g/10 min.),

(c1) dicumyl peroxide (10 hour-half time temperature: 117° C.),

(d1) maleic anhydride, and

(e1) copolymer.

Preparation for the copolymer (e)!

60 parts of polypropylene, 0.1 part of Iruganox 1010 (antioxidant madeby Chiba-Geigy), 1 part of dicumyl peroxide, 10 parts of acrylonitrileand 30 parts of styrene were polymerized in the nitrogen atmosphere at170° C. for 2 hours. After the polymerization, it was sufficientlywashed with acetone and was dried to obtain a copolymer.

The copolymer thus obtained was a graft copolymer comprising a chainconsisting of propylene polymer units and a copolymer chain consistingof acrylonitrile polymer units-styrene polymer units. The chainconsisting of propylene polymer units was 70% by weight, and thecopolymer chain consisting of acrylonitrile polymer units-styrenepolymer units, wherein the weight ratio of the acrylonitrile polymerunits/the styrene polymer units was 28/72 (AN/St=28/72), was 30% byweight. Hereinafter, this is referred to as the copolymer (e1).

A graft copolymer was obtained in the same manner as the copolymer (e1)except that the starting ratio and the starting amounts of acrylonitrileand styrene were changed. The graft copolymer thus obtained comprises50% by weight of the chain consisting of propylene polymer units and 50%by weight of the copolymer chain consisting of acrylonitrile polymerunits-styrene polymer units, wherein the weight ratio of theacrylonitrile polymer units/the styrene polymer units was 25/75(AN/St=25/75). Hereinafter, this is referred to as the copolymer (e2).

A graft copolymer was obtained in the same manner as the copolymer (e1)except that 40 parts of methyl methacrylate were used in place ofacrylonitrile and styrene. The graft copolymer thus obtained comprises70% by weight of the chain consisting of propylene polymer units and 30%by weight of the chain consisting of methyl methacrylate polymer units.Hereinafter, this is referred to as the copolymer (e3).

(1) 40 parts of the above (a1), 60 parts of the above (b1) and 2.5 partsof the above (c1) were blended using Henshel mixer. Thereafter, it wasextruded using a 50 mm single screw extruder at a cylinder temperatureof 250° C. at a die temperature of 300° C. at a rotational speed of 75rpm, and it was supplied into the coating resin vessel maintained at300° C. The melt viscosity of the coating resin comprising the component(a1), (b1) and (c1) was measured using a capillary having the length of2.5 mm and the diameter of 0.25 mm at 300° C. at the shear rate of 1,000sec⁻¹, and it was 95 poise. On the other hand, roving glass fibershaving the fiber diameter of 13 μm were continuously passed through themelted coating resin vessel, and the coating resin was impregnatedbetween the monofilaments. Thereafter, they were passed through the diehaving a diameter of 2.2 mm so that the excess of the resin was removed,and the weight ratio of the resin component/the glass fibers wasadjusted to 30/70. The coated glass fibers thus obtained were cut by arotary cutter to 6 mm. Hereinafter, this is referred to as the coatedglass fibers (B-1).

(2) In the same manner as for (B-1), the coating resin comprising thecomponent (a1), (b1), (c1), (d1) and (e1) in the ratio as shown in Table1, was impregnated into the glass fibers roving, followed by cutting toobtain the coated glass fibers (B-2) to (B-5) having a length of 6 mmand having a weight ratio of the resin component/the glass fibers of30/70. The melt viscosities (poise) of these coating resins are shown inTable 1.

(3) In the same manner as for (B-1), the coating resin of (e1) wasimpregnated into the glass fibers roving, followed by cutting to obtainthe coated glass fibers (B-6) having a length of 6 mm and having aweight ratio of the glass fibers to the resin component of 30/70.

For comparison, without using all of the components (a1), (b1) and (c1),in the same manner as for (B-1), the coated glass fibers (C-1) to (C-3)were obtained. The melt viscosities (poise) of these coating resins areshown in Table 1.

Preparation for the thermoplastic resin coated glass fibers!

(1) 280 parts of chopped strand glass fibers having a length of 3 mm anda fiber diameter of 13 μm were sufficiently impregnated into the mixedsolution comprising 40 parts of acrylonitrile, 60 parts of styrene, 6parts of glycidyl methacrylate and 1 part of benzoyl peroxide.Thereafter, 1,800 parts of water were added thereto, and polymerizationwas carried out at 80° .C for 5 hours. After the polymerization, it waswashed with water well and was dried at 60° C. The amount of the glassfibers in the thermoplastic resin coated glass fibers thus obtained was80% by weight, and the weight ratio between the acrylonitrile polymerunits, the styrene polymer units and the glycidyl methacrylate polymerunits was 27/68/5. Hereinafter, this is referred to as the coated glassfibers (D-1).

(2) Thermoplastic resin coated glass fibers were obtained in the samemanner as for (D-1) except that 12 parts of maleic anhydride was used inplace of glycidyl methacrylate. The amount of the glass fibers in thethermoplastic resin coated glass fibers thus obtained, was 80% byweight, and the weight ratio between the acrylonitrile polymer units,the styrene polymer units and the maleic anhydride polymer units was26/66/8. Hereinafter, this is referred to as the coated glass fibers(D-2).

(3) For comparison, thermoplastic resin coated glass fibers having nofunctional group were obtained in the same manner as for (D-1) withoutusing glycidyl methacrylate. The amount of the glass fibers in thethermoplastic resin coated glass fibers thus obtained was 80% by weight,and the weight ratio of the acrylonitrile polymer units/the styrenepolymer units was 28/72 (AN/St=28/72). Hereinafter, this is referred toas the thermoplastic resin coated glass fibers (E).

EXAMPLE 1

The polymer A and the coated glass fibers (B-1) in the amounts shown inTable 2 (unit: parts), 3 parts of dibutyl tin mercaptide and 0.5 part ofstearic acid were blended using a Henshel mixer. Thereafter, using a 30mm single screw extruder of L/D=24 and a compression ratio=2.3, a flatplate having a thickness of 3 mm and a width of 30 mm, wasextrusion-molded at a cylinder temperature of 165° C. at a dietemperature of 185° C. at a rotational speed of 20 rpm. Theextrusion-molding property, the glass fiber dispersibility, the surfaceappearance and various material properties of the flat plate thusobtained were evaluated by the following method. The results are shownin Table 3.

Extrusion-molding property: evaluated by the screw load (unit; ampere)and the extruded amount (unit: g/min.),

glass fiber dispersibility: three-rank evaluation by visual observation(◯: no glass fiber bundle, Δ: a small amount of glass fiber bundles, X:a large amount of glass fiber bundles),

surface appearance: three-rank evaluation by visual observation (◯:evenly glossy on the surface, and no rough area or external wavinessobserved, Δ: unevenly glossy on the surface, or rough area and externalwaviness observed, X: unevenly glossy on the surface, and rough area andexternal waviness observed),

tensile strength (unit: 10² kg/cm²) and tensile elastic modulus (unit:10² kg/cm²): based on JIS K7113,

flexural strength (unit: 10² kgf/cm²) and flexural elastic modulus(unit: 10² kgf/cm²): based on JIS K7203,

Izod impact strength (with notch) (unit: kg.cm/cm²): based on JIS K7110,

heat distortion temperature (unit: ° C.): based on JIS K7207 (load 18.5kg/cm²), and

moisture resistance (unit: %): evaluated by the tensile strengthretention after a flat molded material was dipped in warm water of 50°C. for 7 days.

EXAMPLES 2 TO 6

The polymer A and the coated glass fibers (B-2) to (B-6) in the amountsshown in Table 2 (unit: part), 3 parts of dibutyl tin mercaptide and 0.5part of stearic acid were blended. In the same manner as Example 1, aflat molded material was produced and was evaluated in various ways. Theresults are shown in Table 3

EXAMPLE 7

The amounts in the amounts shown in Table 2 (unit: part) of the polymerA, the copolymer (e1) and the coated glass fibers (D-1), 3 parts ofdibutyl tin mercaptide and 0.5 part of stearic acid were blended using aHenshel mixer. Thereafter, using a 30 mm single screw extruder of L/D=24and a compression ratio=3.1, a flat plate having a thickness of 3 mm anda width of 30 mm was extrusion-molded at a cylinder temperature of 180°C. at a die temperature of 165° C. at a rotational speed of 7.8 rpm. Theextrusion-molding property, the surface appearance and various materialproperties of the flat plate thus obtained were evaluated and measuredby the following method. The results are shown in Table 4.

EXAMPLES 8 TO 10

The polymer A, the copolymers (e1) to (e3) and the thermoplastic resincoated glass fibers (D-1) and (D-2) in the amounts shown in Table 2(unit: part), 3 parts of dibutyl tin mercaptide and 0.5 part of stearicacid were blended. In the same manner as Example 7, a flat moldedmaterial was produced and was evaluated in various ways. The results areshown in Table 4.

EXAMPLES 11 TO 13

The polymer A and the coated glass fibers (C-1) to (C-3) in the amountsshown in Table 2 (unit: part), 3 parts of dibutyl tin mercaptide and 0.5part of stearic acid were blended. In the same manner as Example 1, aflat molded material was produced and was evaluated in various ways. Theresults are shown in Table 3.

EXAMPLE 14

The polymer A and the chopped strand glass fibers FE not coated with acoating resin obtained by cutting the robing glass fibers to be used forthe coated glass fiber to 6 mm in the amounts shown in Table 2 (unit:part), 3 parts of dibutyl tin mercaptide and 0.5 part of stearic acidwere blended. In the same manner as Example 1, a flat plate moldedmaterial was produced and was evaluated in various ways. The results areshown in Table 3.

EXAMPLES 15 AND 16

The polymer A, the copolymer (e1) and the thermoplastic resin coatedglass fibers (D-1 to (E) in the amounts shown in Table 2 (unit: part), 3parts of dibutyl tin mercaptide and 0.5 part of stearic acid wereblended. In the same manner as Example 7, a flat plate molded materialwas produced and was evaluated in various ways. The results are shown inTable 4.

EXAMPLE 17

The polymer A and the chopped strand glass fibers G having a length of 3mm and a fiber diameter of 13 μm in the amounts shown in Table 2 (unit:part), 3 parts of dibutyl tin mercaptide and 0.5 part of stearic acidwere blended. In the same manner as Example 7, a flat plate moldedmaterial was produced and was evaluated in various ways. The results areshown in Table 4.

Referring to Table 3 and 4, the tensile strength, the tensile elasticmodulus, the flexural strength, the flexural elastic modulus and themoisture resistance are more excellent than those of ComparativeExamples. Particularly, the impact strength is remarkably improved andan extremely excellent mechanical property is shown. The moldability andthe surface appearance are also excellent.

                  TABLE 1                                                         ______________________________________                                        Coated                                                                        glass  Components              Melt                                           fibers (a1)    (b1)    (c1)  (d1)  (e1)  viscosity                            ______________________________________                                        B-1    40      60      2.5   0     0     95                                   B-2    20      80      2.5   0     0     52                                   B-3    40      60      2.5   5     0     120                                  B-4    80      20      2.5   0     10    550                                  B-5    20      80      2.5   5     10    75                                   B-6    0       0       0     0     100   750                                  C-1    100     0       2.5   5     0     2120                                 C-2    0       100     2.5   5     0     35                                   C-3    40      60      0     5     10    920                                  ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                                                            Uncoated                                                                      glass                                     Exam- Polymer    Coated glass fibers                                                                              fibers                                    ples  (A)    (e)     (B)   (C)   (D)    (E) (F)  (G)                          ______________________________________                                        1     100    0       30(B-1)                                                                             0     0      0   0    0                            2     100    0       30(B-2)                                                                             0     0      0   0    0                            3     100    0       30(B-3)                                                                             0     0      0   0    0                            4     100    0       30(B-4)                                                                             0     0      0   0    0                            5     100    0       30(B-5)                                                                             0     0      0   0    0                            6     100    0       30(B-6)                                                                             0     0      0   0    0                            7     100    5(e-1)  0     0     35(D-1)                                                                              0   0    0                            8     100    5(e-1)  0     0     35(D-2)                                                                              0   0    0                            9     100    5(e-2)  0     0     35(D-1)                                                                              0   0    0                            10    100    5(e-3)  0     0     35(D-1)                                                                              0   0    0                            11    100    0       0     30(C-1)                                                                             0      0   0    0                            12    100    0       0     30(C-2)                                                                             0      0   0    0                            13    100    0       0     30(C-3)                                                                             0      0   0    0                            14    100    0       0     0     0      0   19.3 0                            15    100    5(e-1)  0     0     0      35  0    0                            16    100    0       0     0     33.3(D-1)                                                                            0   0    0                            17    100    0       0     0     0      0   0    25                           ______________________________________                                    

                                      TABLE 3                                     __________________________________________________________________________    Examples 1   2   3   4   5   6   11  12  13  14                               __________________________________________________________________________    Screw load                                                                             10  9   11  13  10  10  18  8   16  20                               Extruded amount                                                                        52  55  50  45  51  46  36  47  43  45                               Tensile strength                                                                       8.5 8.1 8.8 8.4 8.3 8.6 6.9 6.5 7.7 5.5                              Tensile elastic                                                                        584 552 602 566 574 550 421 391 458 355                              modulus                                                                       Flexural strength                                                                      11.6                                                                              10.6                                                                              12.1                                                                              11.9                                                                              11.2                                                                              10.8                                                                              9.1 8.8 9.6 7.8                              Flexural elastic                                                              modulus  552 523 576 543 543 532 405 460 488 390                              Impact strength                                                                        19.5                                                                              17.8                                                                              20.5                                                                              15.5                                                                              18.8                                                                              17.9                                                                              5.1 10.5                                                                              8.4 4.1                              Heat deformation                                                                       80.5                                                                              81.3                                                                              81.5                                                                              79.8                                                                              82.5                                                                              81.7                                                                              75.4                                                                              81.5                                                                              78.4                                                                              70.9                             temperature                                                                   Moisture resistance                                                                    99.5                                                                              99.4                                                                              99.9                                                                              99.4                                                                              99.7                                                                              99.5                                                                              82.3                                                                              75.1                                                                              88.1                                                                              69.4                             Surface appearance                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     X   Δ                                                                           X   X                                Glass fiber                                                                            ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     ◯                                                                     X   ◯                                                                     Δ                                                                           X                                dispersibility                                                                __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________    Examples 7   8   9    10  15  16  17                                          __________________________________________________________________________    Screw load                                                                             8   7   8    9   7   18  20                                          Extruded amount                                                                        18.1                                                                              18.6                                                                              17.5 16.8                                                                              18.5                                                                              10.3                                                                              6.1                                         Tensile strength                                                                       11.3                                                                              11.1                                                                              11.0 10.5                                                                              10.5                                                                              9.5 9.1                                         Tensile elastic                                                                        742 739 736  733 731 545 508                                         modulus                                                                       Flexural strength                                                                      18.1                                                                              18.0                                                                              17.4 17.3                                                                              17.6                                                                              12.4                                                                              13.2                                        Flexural elastic                                                                       778 769 768  770 764 562 631                                         modulus                                                                       Impact strength                                                                        29.1                                                                              25.3                                                                              28.4 26.8                                                                              15.9                                                                              5.5 4.6                                         Heat deformation                                                                       80.5                                                                              81.3                                                                              79.9 80.2                                                                              79.8                                                                              73.5                                                                              70.9                                        temperature                                                                   Moisture 99.5                                                                              99.4                                                                              99.1 99.4                                                                              99.1                                                                              88.5                                                                              69.4                                        resistance                                                                    Surface appearance                                                                     ◯                                                                     ◯                                                                     ◯                                                                      ◯                                                                     ◯                                                                     Δ                                                                           X                                           Glass fiber                                                                            ◯                                                                     ◯                                                                     ◯                                                                      ◯                                                                     ◯                                                                     Δ                                                                           X                                           dispersibility                                                                __________________________________________________________________________

We claim:
 1. A composition comprising 100 parts by weight of a vinylchloride polymer (A) and 10 to 200 parts by weight of coated glassfibers (1) coated with a coating resin obtained by melting a componentcomprising a polymer (a) miscible with the vinyl chloride polymer, acrystalline polymer (b) immiscible with the vinyl chloride polymer and aperoxide (c).
 2. The composition according to claim 1, wherein thecoating resin is a resin obtained by melting a component comprising thepolymer (a), the polymer (b), the peroxide (c) and a monomer (d) toimprove an adhesion to the glass fibers.
 3. The composition according toclaim 2, wherein the monomer (d) is a vinyl monomer having a functionalgroup selected from the group consisting of an epoxy group, a carboxylgroup and a carboxyl anhydride group.
 4. The composition according toclaim 1, wherein the polymer (a) is a copolymer of a vinyl cyanidemonomer and an aromatic vinyl monomer, or a methacrylic acid alkyl esterpolymer.
 5. The composition according to claim 1, wherein the polymer(a) is an acrylonitrile-styrene copolymer or polymethyl methacrylate. 6.The composition according to claim 1, wherein the polymer (b) is anolefin polymer.
 7. The composition according to claim 1, wherein thepolymer (b) is polypropylene.
 8. The composition according to claim 1,wherein the melt viscosity of the coating resin is at most 1,000 poise.9. The composition according to claim 1, wherein the coated glass fibers(1) are obtained by continuously passing the glass fibers through thecoating resin in a melt state.
 10. The composition according to claim 1,wherein the amount of the coating resin is 5 to 60% by weight to thecoated glass fibers (1), and is at most 100 parts by weight to 100 partsby weight of the vinyl chloride polymer.
 11. A composition comprising100 parts by weight of a vinyl chloride polymer (A) and 10 to 200 partsby weight of coated glass fibers (2) coated with a coating resin of acopolymer (e) having a polymer chain (X) immiscible with the vinylchloride polymer (A) and a polymer chain (Y) miscible with the vinylchloride polymer in the same molecule.
 12. The composition according toclaim 11, wherein the polymer chain (X) is a polymer chain wherein anolefin monomer is polymerized, and the polymer chain (Y) is a polymerchain wherein a vinyl cyanide monomer and an aromatic vinyl monomer arecopolymerized, or a methacrylic acid alkyl ester monomer is polymerized.13. The composition according to claim 11, wherein the copolymer (e) isa copolymer comprising 95 to 5% by weight of the polymer chain (X) and 5to 95% by weight of the polymer chain (Y).
 14. The composition accordingto claim 11, wherein the amount of the coating resin is 5 to 60% byweight to the coated glass fibers (1), and is at most 100 parts byweight to 100 parts by weight of the vinyl chloride polymer.
 15. Acomposition comprising 100 parts by weight a vinyl chloride polymer (A),1 to 15 parts by weight of a copolymer (e) having a polymer chain (X)immiscible with the vinyl chloride polymer and a polymer chain (Y)miscible with the vinyl chloride polymer in the same molecule, and 10 to150 parts by weight of coated glass fibers (3) coated with a coatingresin of a thermoplastic resin miscible with the vinyl chloride polymer.16. The composition according to claim 15, wherein the thermoplasticresin is a copolymer of 99.5 to 50% by weight of a monomer to form apolymer miscible with the vinyl chloride polymer and 0.5 to 50% byweight of a vinyl monomer having a functional group selected from thegroup consisting of an epoxy group, a carboxyl group and a carboxylicanhydride group.
 17. The composition according to claim 15, wherein thepolymer chain (X) is a polymer chain wherein an olefin monomer ispolymerized, and the polymer chain (Y) is a polymer chain wherein avinyl cyanide monomer and an aromatic vinyl monomer are copolymerized,or a methacrylic acid alkyl ester monomer is polymerized.
 18. Thecomposition according to claim 15, wherein the polymer chain (X) is apolymer chain wherein propylene is polymerized.
 19. The compositionaccording to claim 15, wherein the amount of the coating thermoplasticresin is 5 to 60% by weight to the coated glass fibers (3), and is atmost 100 parts by weight to 100 parts by weight of the vinyl chloridepolymer.